Catalyst manufacture



Sept. 24, 1946. H. v. ATwELL cmnALYsT- MANUFAGTURE Filed May 18, 1944 Ill HAROLD v. ATwELL I VE NTOR Hrs ATrd N'EY Patented Sept. 24, 1946 UNITD STAT aiosnsi CATALYST MANUFACTURE vlilvarold Atwell, Beacon, N. Y., assignor toThe Texas Company, New York, N; Y,,;a corporation of Delaware. ,y d 1 @Application May 1 8, 1,944, seriam- .SSGSQ-g, is claims. (ci. 252-254) The present invention relates to catalyst manufacture, and particularly'to ay .complex liquid'V catalystformedby'reacting a solid metal halide, such as aluminum chloride, with a normally liquid hydrocarbon in the presence of a promoter such as hydrogen halide. r f

Complex .compounds 'formedf by 1. reacting a metal halide with ar petroleum hydrocarbon in the presence of a promoter are usefulas catalysts for electing catalytic conversion of'hydrocarbons such as conversion processes involving valkyla.- tion and isomerization. The metal halide may be reacted with varioustypes of hydrocarbons including olens,paraflins, naphthenes, and aromatics.' A mixture of reactant hydrocarbons may be employed, as for-example,'kerosine or some other fraction of petroleum.

' In accordance with the invention ytheA solid metal halide'is maintained in vay contact zone in lump or granular form. A stream of saturated C4 hydrocarbon in liquid phase is Vpassed through the contact zone incontactvwith the'V solid metal halide underconditions such as to effect solution of a small amount ofthe'vmetal halide in" the liquid stream. The ellluent stream from the con.lv tact zone containingdissolvedmetal halideis subjected to elevated temperature in the presence of hydrogen halideand also in the presence of the normally liquidireactant hydrocarbon in a second zone so as to effect complex formation:

between the metal halide vessel and subjecting the entire mixture to vheating :and stirring in a batch type of operation..

' The present' invention .involves 'a' substantial improvement over the prior vart since it provides for effecting solution of solid metal halidelin'a solvent hydrocarbon underconditions suchtthat substantially :no complex. formationY occurs -fand then effecting reaction Abetween .thefzdissolved halide and Areacta'nt'"hydrocarbons ina separate zone. `f @The invention* thus permits segregating the vconriple'x substantially las rapidly' .it is formed-and also permits" effecting contact between rthe" solvent f hydrocarbon' land the solid metal halidev in the substantial absence of complex. An advantage ofthe process of the present invention is thatfit avoids pumping and circulationiof complex, Whichis particularlyv advanta geus 'iromrvthe standpoint of reducing corrosion ardei'osion of equipment'gf for example,` one serious difliculty'experienced in pumping' 'com-Ly 'plexwithv a reciprpcatingitypeof pump isfthat thecomplex penetratesA thef'packingv glands; and

' 'Ihe reactant hydrocarbon may lbe commingled with the C4 hydrocarbon stream prior to, or subsequent to, its passage through the contact zone, 'although the latter is advantageous, as will be explained later.V Y

The mixture of metal halide and reactant hydrocarbons remain inthe second zone for suilicient time to permit.complexjfcrrnation.`

The resultingr mixturefofv hydrocarbons containinglcomple'x also undergoessettling so. as to effect phase separation between complex andunreacted hydrocarbons.; The hydrocarbon phase comprising mainly C4 4hydrocarbons is*v drawn off in.A acontinuous streamzand recycled through thecontact zone to dissolved additional metal halide after which it-.again passes through the solidies therein ultimately causing" substantial leakage'aswell as injury'to the pump.

`lidvoreover, theuavoidance 'of the presence of complex'in the solution zone permits more effective contact between the solvent hydrocarbon and `the solid metal" halide so that a uniform rate of solution is realized. u The invention also involves a further advantage as regards'the preparation of complex from a metal halide such as aluminum chloride. Aluminum chloride is relatively more solublefin butane than it is vin higher molecular Weight hydrocarbons'. Thus' at a" temperature of about 200 F. normalv butane dissolves about 1.75% aluminum chloride by Weight ofthe butane While normal hexane at the same temperature dissolves only about 0.33%. lNormal butane at a temperature ofl40 F. dissolves about 0.55% by Weight of aluminum chloride YWhile normal hexane vat the sarnetemperature dissolves'only about 0.16%. y Consequently,reither normal or isobutane or a mixture' of both is'used in the present invention to eiectf'solution ofthe solid metal halide and to transfer the dissoivedmetal hande into the "reactionl zone fory reaction with kerosirle4 in which the halide is'much lesssoluble. l y L fThe invention also contemplates iortifying the complex by subjecting it tocontact with a stream u of.`bu.ta`ne ,containing dissolved metal halide, contact being continued until the complex has extracted metalhalide Afrom the solvent hydrocarbon to the extent desired, as will be described later.

In order to describe the invention in more detail, reference Will now `be made to the accompanying drawing which comprises a diagram of iiow useful in preparing a complex of aluminum chloride and kerosine hydrocarbons.

In the drawing the numeral I rdesignates a pair of vessels packed with solidaluminum ,chloe ride in the form of particles or lumps rangingl from about 1A to 1%; inch in diameter. Two vessels are provided so that when one is onstream the other is offstream for recharging with fresh aluminum chloride. j 2

The numeral 2 designates allieating zone which may comprise a tubular heater wherein the mixture of hydrocarbonsk and dissolved aluminunry chloride is raised to the temperature required for effecting complex formation. i f

The numeral 3 designates a reaction and settling vessel. f 1

The numeral 4 designates a heat exchanger; through which the unreacted hydrocarbons are recycled from the vessel 3 Vto either of the ves-- sels I.

An operation in which a butane: stream con,- taining kerosine is' circulatedithrough'the system will be described, rs't. f 1

At the outset andassuming'that'the-vessels-I are packed with solid aluminum chloride,'thesys tem is filled wit-h a mixture -of butane-and kero'- sine, the pressure being suflicient to maintain the butane in liquid phase. The kerosine mayamount. to about l to 15% by volumeV of the butane. The butane and kerosine are drawn from sources not shown through pipes 5 and 6 respectively anddischarged into pipe 'I vwhich leads to the heater 2. The heater 2 is operated so as to heat the hydrocarbon streamto a, teml perature in the range 200 to 300o F. The heated. stream passes through pipe B into the *vessel` 3.. When the vessel 3 becomes filled with liquid, the overflow is conducted through pipe S-by pump I0 which discharges into pipe l-I The pipe Il. communicates with the heat exchanger 4 which in turn discharges into pipe I2.

The. pipe I2 communicates with branch pipes I3 and I4 leading to the vessels l. Y

In this way the hydrocarbon stream is. vintroduced to the top of either of: the. aluminum chloride vessels and ows: downwardly therethrough discharging through pipes. I5 and i6 as the case may be.y which in turn communicatewith thepreviously mentioned pipe 1.

Once the system. has. become lled with hw drocarbon liquid, the introduction of further hydrocarbons may be discontinued. Under such conditions the butane and unreacted kerosine are continuously recirculated through the. system until substantially all. of the kerosine present: is converted to complex. In actual operation it is contemplated that the effluent stream from the aluminum chloride. vessels l will contain a small amount of dissolvedvalurninum chloride and will be substantially free from complex.- Any required makeup promoter is added toYL this stream either prior to or subsequent to its passage to the heater 2. The heating temperature. and the amount of promoter are correlated to eiect substantially complete reaction between the dissolved aluminum chloride and kerosine hydrocarbons. The reaction to` form complex takes place substantially entirely in the. vessel 3 Whichis. of suffi; .cient capacity to permit a substantial reaction time, namely, about to 60 minutes.

The resulting complex settles out and accumulates in the bottom of the vessel 3, while the butane and unreacted kerosine accumulate as a hydrocarbon layer in the upper portion of the vessel 3.

The butane may undergo isomerization so that ultimately the C4 hydrocarbons in the circulating mixture will compriseganequilibrium'mixture of iso and normalbutane. The reaction conditions of time and temperature are such that only a very limited amount of the |butane enters into complex formation with the aluminum chloride.

The hydrocarbon phase separating in the vessel 3 islcontinuously'drawn oi through the pipe 9 and forced'byigthe pump I0 through the pipe I I to the-heatiexchanger 4 wherein the temperasired to a temperature in the range 150 to 200 F.

`-'45 ing rto the heater 2.

` YIt is contemplated maintaining a. relatively short time.l of contact between hydrocarbons and solid aluminum chloride in aluminum chloride vessels t so that' the action taking place therein is essentially that of solution rather than complex formation. Reducing' theltemperature of the. recycled hydrocarbons-in the exchanger 4 is a further means of'- inhibiting complex formation in the-'vessel'|.. 1 The circulation of hydrocarbons through the. system is continued until substantially all ofthe kerosine present is converted to complex. The compleximaybe retained in the vessel 3 until the entire batch of kerosine charged is reacted. 0n the other hand, the complex may be drawn oi. continuously or intermittently if desired.

A modified form'of operation involves charging the system first withbutane a-ndthen adding the kerosine inl small amounts to thecirculating butane stream. In vthis type of operation the kerosine addition to the circulating stream. may be regulated, so asto provide approximately the amount of kerosine required to; react withY the dissolved aluminum chloride in thepstream. pass- Thismethod of operation avoids circulating unreactedkerosine through the aluminum chloride vessels I or at least-reduces the amount so circulated to a minimum.

By circulating the hydrocarbon stream in the `5`0 foregoing manner through the solution vessels complex formation therein can be substantially entirely avoided since under the conditions prevailing therein butane doesnot enter into complex readily.

i The complex formed.. in the. vessel 3 may be drawn off through a, pipey I1 to atower I8 for the purpose of fortifying it with additional aluminum chloride. The complex is advantageously disposed as a static column of liquid in the tower I8.

A stream of butane containing` dissolved aluminum chloride isvdrawn oiiv from the Vessels I` and vconducted through pipe I9 which terminates in a suitable distributor 20 positioned within the bottom of the tower. The butane stream is thusv dispersed within the static column of liquid and rises upwardly therethrough. In doing so thecomplex extracts aluminum chloride from the butane stream until the complexv becomes saturated.

In this way a complex suitableas an isomerization catalyst may be prepared: For'example, a complex catalyst effective for isomerizing normal butaneY is characterized' by havingl a heat of hydrolysis of about 300- tol 330 small calories per T5 gram of complex. The complex leaving the-ves- 1 tane, it is desirable to Y sel 3 may have a heat of hydrolysis of only about 200 to 280 calories. Consequently, its heat of hydrolysis may be raised by fortifying in the tower I6 as already described. This fortifying action is advantageously carried out at a temperature may, if desired, be carried out in a single chamber or vessel.

While specific mention has lbeen made of form- 'ing a complex from aluminum chloride, it is contemplated that other solid metal halides of the Friedel-Crafts type, such as aluminum lbromide and zirconium chloride,.may be used. Likewise, other hydrocarbons or hydrocarbon mixtures than kerosine may be used. However, from the standpoint of making a complex catalyst effectivelfor isomerizing normal parains such as normal buemploy a non-aromatic hydrocarbon.

Obviously many modifications and variations of the invention as above set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims. f

I claim: f

1. A method of preparing a complex catalys formed by reacting aluminum chloride with kerosine hydrocarbons in the presence of hydrogen halide which comprises maintaining aluminum chloride in solid granular form in a contact zone, passing a saturated aliphatic C4 hydrocarbon in liquid phase through the contact zone in contact with said chloride, eiecting solution of a small amount of chloride at a temperature below about 200 F. in the C4 hydrocarbon under conditions such that substantially no complex formation 0ccurs, passing the resultant solution to a reaction zone, subjecting the dissolved chloride to contact in said reaction zone with said kerosine hydrocarbons in the presence of hydrogen chloride at a recyclingv said hydrocarbon phase to the contact aluminum chloride in C4 hydrocarbonsk occurs` zone, and continuing the cyclic operation to eiect substantial conversion of kerosine hydrocarbons to aluminum chloride-hydrocarbon complex.

2. A method of preparing a complex catalyst formed byreacting aluminum chloride with kerosine in the presence of hydrogen halide which comprises maintaining in a contact zone aluminum chloride in solid granular form, circulating through said contact zone in contact with the solid halide a stream of liquid hydrocarbons comprising a major portion of saturated aliphatic C4 hydrocarbon vand a minor portion of kerosine, eiecting contact between solid halide and hydrocarbons under conditions of time and temperature such that solution of a small amount of without substantial complex formation, passing said stream of solution to a reaction zone, subjecting it therein to elevated temperature in the Vrange of about 200 to 300ov F. and in the presence of hydrogen halide such that dissolved aluminum chloride reacts with kerosine hydrocarbons to .form complex, separating resulting complex fromV the unreacted hydrocarbons including C4 hydrocarbons, recycling the hydrocarbons from which complex has been separated to the contact zone; and continuing the circulation of hydrocarbons to effect substantial conversion of said kerosine K through said contact zone in contact with thev solid halide `a stream of saturated aliphatic C4 hydrocarbons in liquid phase, effecting contact between'solid halide and C4 hydrocarbons under conditions of time and temperature such that solution of a small amount of aluminum chloride in C4 hydrocarbons occurs without substantial complex formation, thereafter vpassing the circulating stream containing dissolved aluminum chloride to a reaction zone, adding to the stream, passing to said reaction zone a small amount of kerosine, subjecting the dissolved chloride to contact with the kerosine in the presence of hydrogen halide at elevated temperature Vsuch that dissolved aluminum chloride reacts With kerosine to form complex, separating resulting complex from the unreacted hydrocarbons including C4 hydrocarbons, recycling the hydrocarbons from which complex has been separated to the contact zone, and continuing the circulation of hydrocarbons to effect substantial conversion of kerosine hydrocarbons to complex.

HAROLD V. ATWELL. 

